Polyurea thickening nonionic surfactant detergent and preparation method thereof

Abstract

The invention relates to a polyurea thickening nonionic surfactant detergent. The polyurea thickening nonionic surfactant detergent comprises the following components in percentage by mass: 15-35% of a nonionic surfactant, 0.5-3% of modified polyurea, 0.5-4% of protease, 0.5-1% of a softener, 0.1-5% of a washing assistant and the balance of water. The added modified polyurea can obtain a pseudo-polymer with low solubility through hydrogen-bond interaction and hydrophobic association, fine micelle aggregates are separated out, a three-dimensional network structure is constructed, liquid flow is effectively limited, gel is formed, and the thickening effect is achieved. Polyurea is modified through methoxy polyethylene glycol, so that hydrophobicity and hydrophilicity of the modified polyurea are matched, and fine micelle aggregates can be separated out more easily to form a three-dimensional network structure; meanwhile, the modified polyurea has a star-shaped structure, and a more stable three-dimensional network structure can be formed, so that a good thickening effect is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of detergents, in particular to a polyurea thickened nonionic surfactant detergent and a preparation method thereof. Background Art

[0002] Polyurea is a new type of solvent-free, pollution-free, green and environmentally friendly polymer material developed in recent years. The functions of polyurea in detergents mainly include softening, thickening, improving rheology, and anti-redeposition. Polyurea is a polymer material with urea bonds generated by the reaction of isocyanate components and amino compound components. After polyurea is cured into a film, the type of chemical bonds contained in the molecular chain of polyurethane is the same or similar. Therefore, polyurea is also called a special polyurethane or polyurethane with high mechanical properties. Because polyurethane has surfactant properties, it can form micelles in water. In the aqueous phase system, the hydrophobic segments of polyurethane aggregate with the hydrophobic segments, so that the polyurethane macromolecular segments produce intramolecular and intermolecular associations to form micelles.

[0003] Generally, laundry detergent is a combination of ionic surfactants and nonionic surfactants, among which ionic surfactants are mainly anionic surfactants with a large content. Since nonionic surfactants can emulsify dirt on fabrics, anionic surfactants can reduce the surface tension of water and increase permeability, making it easier for dirt to fall off, and anionic / nonionic surfactants will not produce adsorption effects. This type of compound system can form a mixed micelle structure, which has the effect of increasing or decreasing the solubilization of micelles. This type of laundry detergent can form a more stable structure and has better performance in emulsification, washing and decontamination. Cationic surfactants have no washing function, but have functions such as sterilization, mildew prevention, antistatic, and softening, and are also commonly used in detergents. When cationic surfactants are added to the formula, the cations and anions will combine, and it is easy to produce insoluble salts that precipitate from the solution, so they lose surface activity, affect the micelle structure, and thus destroy the stability of the product.

[0004] Nonionic surfactants do not ionize themselves and can be mixed with other types of surfactants. They have good compatibility and good solubility in various solvents. When only nonionic surfactants are present in the laundry detergent formula, the viscosity of the product is low. The national standard does not have viscosity requirements, but consumers often look at the viscosity when purchasing. If the product viscosity is too low, it will affect consumers' purchase choice of laundry detergent products. Adjusting the viscosity of the laundry detergent to an appropriate range can improve the fluidity of the laundry detergent, make it easier for consumers to use and dissolve, and make it easier to control the dosage.

[0005] Based on this, it is urgent to propose a technical solution to solve the above-mentioned problems. Summary of the invention

[0006] Based on this, the present invention develops a polyurea thickening nonionic surfactant detergent and a preparation method thereof, and the modified polyurea obtained by the modification of polyurea has the advantages of strong thixotropy, stable storage, non-viscous, easy to use, good anti-settling and anti-sagging performance. It can generate supramolecular polymers in the system, and the pseudo-polymer solubility obtained is low, and it is easy to precipitate out to form fine micelle aggregates with high aspect ratio, and such micelle aggregates overlap to form a three-dimensional network structure, which limits the flow and gel of the liquid, and forms a clear and transparent stable solution with a certain viscosity, so as to achieve the effect of thickening of the nonionic surfactant system, improve the defects of conventional laundry detergent products such as mildew resistance, suppleness, antibacterial, and antistatic, and the product can be adjusted to an ideal viscosity. The present invention uses modified polyurea to form micelle aggregates in water, and then forms a three-dimensional network structure, so as to achieve the effect of the detergent composed of nonionic surfactants with suitable viscosity.

[0007] One object of the present invention is to provide a polyurea thickened nonionic surfactant detergent, wherein the polyurea thickened nonionic surfactant detergent comprises the following components in mass fraction:

[0008]

[0009] in,

[0010] The modified polyurea is an adduct intermediate obtained by reacting toluene diisocyanate with methoxy polyethylene glycol pretreated with methanesulfonic acid, and reacting with 2,4,6-triethyl-1,3,5-benzenetrimethylamine having a star-shaped structure.

[0011] Furthermore, the nonionic surfactant is a nonionic surfactant having an ethoxy structure.

[0012] Furthermore, the nonionic surfactant is selected from one or more of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid ethoxylate or polyol polyoxyethylene ether fatty acid ester.

[0013] Furthermore, the softener is selected from one or more of ester-based quaternary ammonium salts or polyquaternary ammonium salts.

[0014] Furthermore, the detergent aid is selected from one or more of preservatives, anti-redeposition agents, fragrances, pigments, alkali metal halide salts or pH regulators.

[0015] Another object of the present invention is to provide a method for preparing the above-mentioned polyurea thickened nonionic surfactant detergent, comprising the following steps:

[0016] S1, mixing toluene diisocyanate and ethyl acetate, stirring and heating, then adding pretreated methoxy polyethylene glycol, stirring and reacting to obtain a monoisocyanate adduct intermediate;

[0017] S2, mixing lithium nitrate, 2,4,6-triethyl-1,3,5-benzenetrimethylamine and N-methylpyrrolidone, stirring and heating, then adding the monoisocyanate adduct intermediate, stirring and reacting, purifying, and obtaining a modified polyurea;

[0018] S3, heating the water, adding nonionic surfactant, and stirring evenly;

[0019] S4, add modified polyurea and stir until completely dissolved;

[0020] S5. Add detergent, protease and softener, and stir until completely dissolved;

[0021] S6. After cooling, adjust the pH to obtain a polyurea thickened nonionic surfactant detergent.

[0022] Furthermore, in step S1, the heating temperature is 30-50°C.

[0023] Furthermore, in step S2, the heating temperature is 70-90°C.

[0024] Furthermore, in step S6, the pH is 6.0-8.0.

[0025] The present invention has the following beneficial effects:

[0026] (1) The modified polyurea is added to the detergent in the present invention, which has a good thickening effect. The modified polyurea is obtained by first reacting toluene diisocyanate with pretreated methoxy polyethylene glycol to generate a monoisocyanate adduct intermediate, and then reacting with 2,4,6-triethyl-1,3,5-benzenetrimethylamine having a star-shaped structure. This component can obtain a pseudo-polymer with low solubility through hydrogen bonding and hydrophobic association, and precipitate to form fine micelle aggregates with a high aspect ratio. These micelle aggregates can further construct a three-dimensional network structure, effectively restrict the flow of the liquid, form a gel and achieve a thickening effect; at the same time, the three-dimensional network structure of the component exists in the composition for a long time and stably, and can self-heal into a new three-dimensional network structure after being destroyed, thereby avoiding the solution viscosity from becoming thinner.

[0027] (2) The present invention modifies polyurea by methoxy polyethylene glycol, so that the modified polyurea matches hydrophobicity and hydrophilicity, has a suitable solubility in water, and is more likely to precipitate small micelle aggregates to form a three-dimensional network structure, thereby achieving system thickening; at the same time, the modified polyurea has a star-shaped structure, and therefore has a higher physical crosslinking density. Compared with linear polyurea molecules, it can form a more stable three-dimensional network structure, which limits the movement of molecular chains, enhances the viscosity of the system, and achieves a thickening effect. In addition, the star-shaped structure increases the specific surface area of ​​the polymer, which is conducive to improving its compatibility and binding ability with other components, further enhancing the thickening effect.

[0028] (3) The present invention uses a nonionic surfactant having an ethoxy structure, which has good compatibility with the ethoxy structure of the modified polyurea and can enhance the thickening effect of the modified polyurea.

[0029] (4) The modified polyurea and quaternary ammonium salt type cationic softener are used simultaneously in the present invention to reduce the surface tension of the solution, play a synergistic role in enhancing the wettability of the washing product, and enhance the softening effect of the washing product. DETAILED DESCRIPTION

[0030] In order to more clearly illustrate the technical solution of the present invention, the following examples are listed. Unless otherwise stated, the raw materials, reactions and post-treatment methods shown in the examples are common raw materials on the market and technical methods well known to those skilled in the art.

[0031] The words "preferred", "preferably", "more preferably", etc. in the present invention refer to embodiments of the present invention that can provide certain beneficial effects in certain circumstances. However, other embodiments may also be preferred under the same circumstances or other circumstances. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not applicable, nor is it intended to exclude other embodiments from the scope of the present invention.

[0032] It should be understood that, except in any operating examples, or where otherwise indicated, all numbers indicating, for example, the amounts of ingredients used in the specification and claims should be understood to be modified in all cases by the term "about". Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximate values ​​that vary depending on the desired properties to be obtained by the present invention.

[0033] The methoxy polyethylene glycol in the examples and comparative examples of the present invention is methoxy polyethylene glycol 350 and methoxy polyethylene glycol 500, which are purchased from Shanghai Titan Technology Co., Ltd.

[0034] The nonionic surfactant in the examples and comparative examples of the present invention is AEO-9, purchased from BASF.

[0035] The protease in the examples and comparative examples of the present invention is alkaline protease purchased from Novozymes.

[0036] The softener in the embodiments and comparative examples of the present invention is polyquaternium salt, with the brand name SC133, purchased from Dow.

[0037] The preservative in the examples and comparative examples of the present invention is Kathon, brand Nipaguard CG, purchased from Clariant.

[0038] The anti-redeposition agent in the examples and comparative examples of the present invention is sodium polyacrylate, with the brand name ACUSOL445N, purchased from Dow.

[0039] The pretreatment method of methoxy polyethylene glycol in the embodiments of the present invention and the comparative examples comprises the following steps:

[0040] 0.063 g of methanesulfonic acid and 42 g of methoxy polyethylene glycol were mixed, vacuum dried at 120° C. for 2 h, cooled to room temperature, and sealed with nitrogen to obtain pretreated methoxy polyethylene glycol.

[0041] The components and their corresponding mass fractions in the embodiments of the present invention and the comparative examples are shown in Table 1:

[0042] Table 1 The components and corresponding mass fractions in Examples 1-3 and Comparative Examples 1-2

[0043]

[0044] The preparation method of the above-mentioned polyurea thickened nonionic surfactant detergent comprises the following steps:

[0045] S1, 17.42g toluene diisocyanate and 8.71g ethyl acetate were mixed, stirred and heated to 45°C, and then 34g pretreated methoxy polyethylene glycol 350 and 4.5g pretreated methoxy polyethylene glycol 500 were added, and stirred to react to obtain a monoisocyanate adduct intermediate;

[0046] S2, 2.33 g of lithium nitrate, 7.48 g of 2,4,6-triethyl-1,3,5-benzenetrimethylamine and 64.38 g of N-methylpyrrolidone were mixed, stirred and heated to 80° C., then the monoisocyanate adduct intermediate was added, stirred for reaction, and ethyl acetate was removed by reduced pressure distillation to obtain a modified polyurea;

[0047] S3. According to the above mass fraction, heat the deionized water to 60°C, add AEO-9, and stir evenly;

[0048] S4, adding the modified polyurea and stirring until completely dissolved;

[0049] S5. Add detergent, protease and softener, and stir until completely dissolved;

[0050] S6. Cool down to 40° C., add citric acid to adjust the pH to 7.5, and obtain a polyurea thickened nonionic surfactant detergent.

[0051] Comparative Example 1

[0052] A polyurea thickened nonionic surfactant detergent. The difference between this comparative example and Example 1 is that in step S1, unpretreated methoxy polyethylene glycol is added, and other ingredients and preparation methods are the same as those in Example 1.

[0053] Comparative Example 2

[0054] A polyurea thickened nonionic surfactant detergent. The difference between this comparative example and Example 1 is that in step S2, 2,4,6-triethyl-1,3,5-benzenetrimethylamine is replaced by meta-xylylenediamine, and other ingredients and preparation methods are the same as those in Example 1.

[0055] Test Example 1

[0056] The detergents prepared in Example 1 and Comparative Examples 1-2 were subjected to stability tests.

[0057] Test method:

[0058] Low temperature stability test: After the detergents are bottled and sealed, they are placed in an environment with a temperature of 0±2℃. After being kept at a constant temperature for 2 months, they are taken out and restored to room temperature to observe the appearance. If the sample does not delaminate, has no flocs or precipitation, and has no obvious change in color, it is judged to be qualified for low temperature stability.

[0059] Test of room temperature stability: After the detergents are bottled and sealed, they are placed in an environment with a temperature of 25±2℃. After being placed at a constant temperature for 2 months, take them out and immediately observe their appearance. If the samples do not delaminate, have no flocs or precipitation, and have no obvious changes in color, they are judged to be qualified for room temperature stability.

[0060] High temperature stability test: After the detergents are bottled and sealed, they are placed in an environment with a temperature of 45±2℃. After being kept at a constant temperature for 2 months, they are taken out and restored to room temperature to observe the appearance. If the samples do not delaminate, have no flocs or precipitation, and have no obvious changes in color, they are judged to be qualified for high temperature stability.

[0061] The test results are shown in Table 2:

[0062] Table 2 Detergent stability test results prepared in Example 1 and Comparative Examples 1-2

[0063] project Example 1 Comparative Example 1 Comparative Example 2 Low temperature stability qualified qualified Failure Room temperature stability qualified qualified qualified High temperature stability qualified Failure Failure

[0064] The above test results show that the sample prepared in Example 1 has no stratification, no floccules or precipitation, and no obvious change in color after being placed at different temperatures for 2 months, and has good stability. The addition of modified polyurea has no obvious effect on the stability of the product. In Comparative Example 1, untreated methoxy polyethylene glycol is added, so that the sample has stratification and floccules at high temperature; in Comparative Example 2, 2,4,6-triethyl-1,3,5-benzenetrimethylamine is replaced with m-phenylenediamine, and the sample has stratification and turbidity at low temperature, and discoloration at high temperature, and has poor stability.

[0065] Test Example 2

[0066] After completing the stability test, the detergent samples prepared in Example 1 and Comparative Examples 1-2 were returned to room temperature for viscosity testing.

[0067] Test method: Use a viscometer to test the viscosity of each detergent sample. Use rotor No. 2, select a speed of 30 rpm, keep the sample at a constant temperature of 25°C, and use a viscosity unit of mPa.s.

[0068] The test results are shown in Table 3:

[0069] Table 3 Viscosity test results of the detergents prepared in Example 1 and Comparative Examples 1-2 after completing stability tests

[0070] Viscosity value (mPa·s) Example 1 Comparative Example 1 Comparative Example 2 Low temperature 860.79 680.77 622.31 normal temperature 835.23 654.25 640.89 high temperature 898.55 661.13 638.67

[0071] The above test results show that after the stability test, the viscosity of Example 1 does not change much, and the system can still maintain a high viscosity due to the stable three-dimensional network structure and star-shaped structure. In Comparative Example 1, unpretreated methoxy polyethylene glycol is added when preparing modified polyurea, and in Comparative Example 2, 2,4,6-triethyl-1,3,5-benzenetrimethylamine is replaced with m-phenylenediamine. The stability of the three-dimensional network structure formed by the system is worse than that of the present invention, so the viscosity is lower than that of the present invention.

[0072] Test Example 3

[0073] The detergents prepared in Example 1 and Comparative Examples 1-2 were tested for fluidity.

[0074] Test method: On the same piece of pure cotton clothing, trim and take out a piece of fabric with a length of 10cm*10cm, and mark the center position for use. Prepare 3 pieces each, test the samples of each formula in parallel 3 times, and record the average value. Tilt a wooden board at 45 degrees, and stick the prepared first piece of fabric flat on the board. When testing the second and third pieces of fabric, stick them in the same position as the first piece of fabric. Then, use a detergent pump head of the same specification, press 1 pump of detergent sample in the center position of the marked fabric, observe the flow of the sample, and use a timer to record the time required for the detergent sample to just flow out of the fabric, and repeat the test for other detergent samples. The longer the time, the higher the viscosity of the detergent sample, the thicker it is, the more fluid it has, and the more it can reach the required viscosity.

[0075] The test results are shown in Table 3:

[0076] Table 4 Fluidity test results of detergents prepared in Example 1 and Comparative Examples 1-2

[0077] project Example 1 Comparative Example 1 Comparative Example 2 No. 1 6.5s 4s 3s No. 2 7.0s 3.5s 3s No. 3 6.5s 3.5s 3.5s average value 6.67s 3.67s 3.17s

[0078] The above test results show that the addition of modified polyurea to the detergent in Example 1 improves the viscosity of the detergent, and the flow time is longer, the viscosity is higher, the detergent has a certain fluidity, and the compatibility and bonding ability between the components are good. Comparative Examples 1-2 have a shorter flow time, and the viscosity of the detergent is lower and thinner.

[0079] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0080] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A polyurea thickened nonionic surfactant detergent, It is characterized in that The polyurea thickening nonionic surfactant detergent comprises the following components by mass fraction: in, The modified polyurea is an adduct intermediate obtained by reacting toluene diisocyanate with methoxy polyethylene glycol pretreated with methanesulfonic acid, and reacting with 2,4,6-triethyl-1,3,5-benzenetrimethylamine having a star-shaped structure.

2. The polyurea thickened nonionic surfactant detergent according to claim 1, It is characterized in that The nonionic surfactant is a nonionic surfactant with an ethoxy structure.

3. The polyurea thickened nonionic surfactant detergent according to claim 2, It is characterized in that The nonionic surfactant is selected from one or more of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid ethoxylate or polyol polyoxyethylene ether fatty acid ester.

4. The polyurea thickened nonionic surfactant detergent according to claim 1, It is characterized in that The softener is selected from one or more of ester-based quaternary ammonium salts or polyquaternary ammonium salts.

5. The polyurea thickened nonionic surfactant detergent according to claim 1, It is characterized in that The detergent aid is selected from one or more of preservatives, anti-redeposition agents, fragrances, pigments, alkali metal halide salts or pH regulators.

6. A method for preparing the polyurea thickened nonionic surfactant detergent according to any one of claims 1 to 5, It is characterized in that The steps include: S1, mixing toluene diisocyanate and ethyl acetate, stirring and heating, then adding pretreated methoxy polyethylene glycol, stirring and reacting to obtain a monoisocyanate adduct intermediate; S2, mixing lithium nitrate, 2,4,6-triethyl-1,3,5-benzenetrimethylamine and N-methylpyrrolidone, stirring and heating, then adding the monoisocyanate adduct intermediate, stirring and reacting, purifying, and obtaining a modified polyurea; S3, heating the water, adding nonionic surfactant, and stirring evenly; S4, add modified polyurea and stir until completely dissolved; S5. Add detergent, protease and softener, and stir until completely dissolved; S6. After cooling, adjust the pH to obtain a polyurea thickened nonionic surfactant detergent.

7. The method for preparing the polyurea thickened nonionic surfactant detergent according to claim 6, It is characterized in that In step S1, the heating temperature is 30-50°C.

8. The method for preparing the polyurea thickened nonionic surfactant detergent according to claim 6, It is characterized in that In step S2, the heating temperature is 70-90°C.

9. The method for preparing the polyurea thickened nonionic surfactant detergent according to claim 6, It is characterized in that In step S6, the pH is 6.0-8.0.

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